The subject matter of the present invention includes new 4,5-diaminopyrazole compounds and their physiologically compatible salts with organic or inorganic acids. The subject matter of the present invention also includes dye compositions containing these new compounds as dyestuff pre-cursor compounds.
Oxidation dyestuffs have been important in the field of traditional hair dyeing for a long time. The effective dyeing agent is produced by reaction of certain developer and coupler substances in the presence of an oxidizing agent. Hair dye compositions for dyeing hair natural color shades are of special significance. Besides those dye compositions combinations of suitable oxidation dye precursor compounds are used to produce currently fashionable color nuances and accents. Currently brown shades with outstanding aubergine or copper tones, especially glowing red tones that deviate from natural colors, can be produced.
Oxidation dyestuffs, which are used for treatment of human hair, have very stringent requirements besides the requirements for producing certain predetermined color effects. The dyestuff must be both toxicologically and dermatologically unobjectionable and also not sensitizing. A broad palette of different color shades and nuances are required, which must be obtained by suitable combination of appropriate developer and coupler components. The hair dyeing compositions obtained should have good wash-fastness, light-fastness, sweat-fastness, permanent wave-fastness, acid-fastness, base-fastness and friction-fastness. In each case these hair dye compositions must remain stable under the common current daily conditions for at least four to six weeks.
In the past 4-aminophenol was the predominant developer used to cover the increasingly important red range. Pyridine derivatives and pyrimidine derivatives, which generally are not satisfactory for dyeing, have also been employed because of considerations regarding the physiological compatibility of 4-aminophenol. A significant improvement in the color stability, especially in the red range, was obtained by the exchange of p-aminophenol by the 4,5-diaminopyrazole compounds described in German Patent Applications DE-OS 42 34 885, DE-OS 42 34 887 and EP-OS 0 375 977. The manufacture of these latter dye compounds by the methods described in those applications is however, in part, very expensive and requires, in part, starting materials, which are expensive and not widely available. 4,5-diaminopyrazoles substituted in the 3 position are known from EP-OS 0 740 931. These compounds however must be made, in part, according to an expensive method, since components, especially C3 components, are not readily available. The pyrazoles described in EP-OS 0 740 931 are also not entirely satisfactory in regard to the attainable color palette and color saturation.
While most oxidation dyestuffs are characterized by hardly any weakening or impairment on undamaged hair, serious differences result when they are used on damaged hair. The hairstylist knows from his daily practice that dyestuffs are not absorbed uniformly on the hair to be dyed. While the hair roots are usually intact, the hair tips are generally damaged because of the effects of weather, frequent washing and combing as time goes on. The damage increases from the roots to the tips. A non-uniform color is thus produced from the roots to the tips when the hair is dyed because of the non-uniform condition of the hair from the roots to the tips. An additional problem is that the absorbed dyestuffs are more easily washed from the damaged part of the hair than from the undamaged part of the hair. As a result after a few washings of the dyed hair the differences in the color of the dyed damaged part of the hair and the dyed undamaged part of the hair are more clearly visible.
Thus there is a great long-standing need for new dye precursor compounds suitable for oxidative dye systems for coverage of the red range, which provide a considerably improved color stability against shampooing on hair of different quality, especially on hair that has been damaged by permanent shaping and bleaching, besides good absorption properties. It is an object of the present invention to provide these new dye precursor compounds.
Certain special new bridged pyrazole compounds attain this object in an outstanding manner.
The subject matter of the present invention thus includes the bridged 4,5-diaminopyrazole compounds of formula (I) or their salts with organic or inorganic acids: 
wherein
R1 represents hydrogen, a straight-chain or branched C1- to C6-alkyl group, a C1- to C4-hydroxyalkyl group, a C1- to C4-aminoalkyl group, a C1- to C8-alkylamino group, a di(C1- to C8-alkyl)amino group, a C1- to C4-alkylamino-(C1- to C4-alkyl) group or a di(C1- to C4-alkylamino)- C1- to C4-alkyl group, an aryl group or a heteroaryl group;
R2 and R3, independently of each other, are the same or different and each represent hydrogen, a straight-chain or branched C1- to C6-alkyl group, an aryl group, a heteroaryl group, a carboxylic acid group, a carboxylic acid ester group, an unsubstituted or substituted carboxylic acid amide group, a hydroxy group or a C1- to C4-hydroxyalkyl group, or R2 and R3 together represent an unsubstituted or substituted C1- to C6-alkylene group;
Z represents a C1- to C10-alkyl diradical, which is optionally interrupted by a heteroatom, for example by a nitrogen atom, an oxygen atom or a sulfur atom, an aromatic or heteroaromatic diradical, which may be substituted optionally with a hydroxy group or a C1- to C6-alkyl group and/or may be subjected to a benzo-condensation once or twice; or a diradical of formula xe2x80x94Ar(Alk)nxe2x80x94Arxe2x80x94, wherein Ar represents an arylene group or a heteroarylene group (especially a phenylene group or a pyridylene group), which may optionally be substituted, Alk represents a xe2x80x94CH2xe2x80x94 group and n represents a number from 0 to 6; and x and y independently of each other represent 0 or 1.
The following bridged pyrazole compounds of formula (I) are, for example, suitable: 
Compounds of the general formula (I), in which R1 is a hydrogen atom, a methyl group, a phenyl group, a thienyl group or a furyl group; R2 and R3, independently of each other, each represent a hydrogen atom, a phenyl group, a carboxylic acid amide group or a hydroxymethyl group; Z represents an unsubstituted alkylene diradical, phenylene diradical or heteroaryl diradical, and x and y each represent, independently of each other, 0 or 1, are especially preferred as dye compounds of the invention and in the dye compositions of the invention.
Compounds of formula (I), in which R1 to R3 each represent a hydrogen atom; Z represents an unsubstituted alkylene diradical, phenylene diradical or heteroaryl diradical, and x and y each represent, independently of each other, 0 or 1, are especially preferred as dye compounds of the invention and in the dye compositions of the invention.
The compounds of formula (I) can be made with different methods.
One possible synthesis schema 1 is described hereinbelow. First two equivalents of 3,5-dibromo-4-nitropyrazole are bridged with a dihalogenide. After conversion to the corresponding 5-benzylamino compound and subsequent catalytic hydrogenation one obtains the corresponding 4,5-diaminopyrazole of the general formula (I). 
However in the case of certain embodiments the preparative schema 2 is advantageous. In the method of schema 2 first cyanoethyl hydrazine is reacted with dialdehydes or diketones to form the corresponding dihydrazones. Subsequently the dihydrazones so obtained are cyclized to form the bridged 5-aminopyrazoles. The intermediate steps in the method are performed, for example, according to the procedure set forth in FR-A 1 403 372. The subsequent introduction of the second pyrazole amino group into position 4, which for example is possible by azo coupling or nitrosation, similarly makes 4,5-diaminopyrazoles of the general formula (I) available. This synthesis schema 
preferably starts with the aldehydes.
The 5-benzylamino-3-bromo compounds from schema 1 could be employed for introduction of a substituent in the 3 position of the pyrazole. Ideally this can occur according to Schema 3, for example, by Suzuki coupling, in which additional coupling reactions are conceivable. 
Because of the oxidation sensitivity of the 4,5-diaminopyrazole compounds according to the invention the compounds of formula (I) are preferably isolated as free acid adducts instead of free bases for reasons of improved handling. The salts so obtained are predominantly oxygen insensitive. In organic or organic acids can be used for this purpose. For example, citric acid, tartaric acid and especially hydrochloric and sulfuric acids are preferable.
The compounds of formula (I) are predominantly suitable as dye precursor compounds in an oxidative system for dyeing keratin fibers. Although the compounds of formula (I) are especially suitable for dyeing keratin fibers, for example wool, silk or hair, especially human hair, they can also be used for dyeing other natural or synthetic fibers, especially cotton or nylon 66.
The subject matter of the present invention also includes a composition for oxidative dyeing of keratin fibers, especially hair, which is characterized by a content of at least one 4,5-diaminopyrazole of the general formula (I), or a salt thereof with an organic or inorganic acid.
The 4,5-diaminopyrazole of formula (I) is contained in the dye compositions according to the invention in an amount of about 0.005 to 20 percent by weight. However the preferred amount of the 4,5-diaminopyrazole of formula (I) in the dye composition according to the invention is from about 0.01 to 10 percent by weight and especially from about 0.1 to 6 percent by weight.
The compounds of formula (I) can be used both alone and also in combination with the known developer and/or coupler substances, which usually are found in oxidative dye system for dyeing fiber materials.
The following known coupler substances are particularly suited for the composition according to the invention:
N-(3-dimethylaminophenyl)-urea, 2,6-diamino-pyridine, 2-amino-4-[(2-hydroxyethyl)amino]-anisole, 2,4-diamino-1-fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di[(2-hydroxyethyl)amino]-1, 5-dimethoxy-benzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)pyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene, 2,4-diamino-1-(3-hydroxypropoxy)-benzene, 2,4-diamino-1-(3-methoxypropoxy)-benzene, 1-(2-aminoethoxy)-2,4-diaminobenzene, 2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene, 2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]aniline, 4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene, 5-methyl-2-(1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline, 3-[(2-aminoethyl)-amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane, di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxybenzene, 2,6-bis(2-hydroxyethyl)aminotoluene, 4-hydroxyindole, 3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-aminophenol, 2-[(3-hydroxyphenyl)amino]-acetamide, 5-[(2-hydroxyethyl)-amino]-2-methylphenol, 3-[(2-hydroxy-ethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol, 5-amino-2-ethylphenol, 2-(4-amino-2-hydroxyphenoxy)ethanol, 5-[(3-hydroxypropyl)amino]-2-methylphenol, 3-[(2,3-dihydroxypropyl)-amino]-2-methylphenol, 3-[(2-hydroxyethyl)-amino]-2-methylphenol, 2-amino-3-hydroxypyridine, 5-amino-4-chloro-2-methylphenol, 1-naphthol, 1,5-dihydroxynapthalene, 1,7-dihydroxynapthalene, 2,3-dihydroxynapthalene, 2,7-dihydroxynapthalene, 2-methyl-1-naphthol acetate, 1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 1,3-dihydroxy-2,4-dimethylbenzene, 3,4-methylendioxyphenol, 3,4-methylendioxyaniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxol, 6-bromo-1-hydroxy-3,4-methylendioxybenzene, 3,4-diaminobenzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazoleone, 5,6-dihydroxyindole, 5,6-dihydroxyindoleine, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole and 2,3-indoleindione, or their salts.
For production of natural and fashionable red shades it is especially advantageous to combine the compounds of formula (I) with additional developer substances. The additional developer substances include p-phenylenediamines, p-aminophenols and other 4,5-diaminopyrazoles or their salts.
Particularly the following additional developer substances are preferred for inclusion in the compositions of the invention:
1,4-diaminobenzene (p-phenylendiamine), 1,4-diamino-2-methylbenzene (p-toluylenediamine), 1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene, 2-chloro-1,4-diaminobenzene, 4-phenylaminoaniline, 4-dimethylaminoaniline, 4-diethylaminoaniline, 4-[di(2-hydroxyethyl)amino]aniline, 4-[(2-methoxyethyl)amino]aniline, 4-[(3-hydroxypropyl)amino]-aniline, 1,4-diamino-2-(2-hydroxyethyl)benzene, 1,4-diamino-2-(1-hydroxyethyl)benzene, 1,4-diamino-2-(1-methylethyl)benzene, 1,3-bis-[(4-aminophenyl)-(2-hydroxyethyl)amino]-2-propanol, 1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-aminophenol, 4-amino-3-methylphenol, 4-methylaminophenol, 4-amino-2-(aminomethyl)phenol, 4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol, 4-amino-2-(methoxymethyl)phenol, 4-amino-2-(2-hydroxyethyl)phenol, 5-aminosalicylic Acid, 2,5-diaminopyridine, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-(1H)pyrimidone, 4,5-diamino-1-(2-hydroxy-ethyl) -1H-pyrazole, 4,5-diamino-1-(1-methylethyl)-1H-pyrazole, 4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole, 1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole, 4,5-diamino-1-methyl-1H-pyrazole, 4,5-diamino-3-methyl-1-phenyl-1H-pyrazole, 4,5-diamino-1-(2-hydroxyethyl)-3-methyl-1H-pyrazole, 2-aminophenol, 2-amino-6-methylphenol and 2-amino-5-methylphenol or their salts.
The known developer substances and coupler substances are contained in the composition according to the invention in a total amount of from about 0.01 to 20 percent by weight, preferably about 0.2 to 6 percent by weight.
The compounds of formula (I) understandably can be employed in combination with conventional anionic, cationic, zwitterionic or nonionic dyestuffs.
Suitable anionic dyestuffs include, for example, the following:
6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalene sulfonic acid disodium salt (Cl 15985; Food Yellow No. 3; FDandC Yellow No. 6), 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (Cl 10316; Acid Yellow No. 1; Food Yellow No. 1), 2-(indan-1,3-dion-2-yl)quinoline-x,x-sulfonic acid (mixture of mono and disulfonic acid) (Cl 47005; DandC Yellow No. 10; Food Yellow No. 13, Acid Yellow No. 3), 5-hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo]-pyrazole-3-carboxylic acid trisodium salt (Cl 19140; Food Yellow no. 4; Acid Yellow No. 23), 9-(2-carboxyphenyl)-6-hydroxy-3H-xanthen-3-one (Cl 45350; Acid Yellow No. 73; DandC Yellow No. 8), 5-[(2,4-dinitrophenyl)amino]-2-phenylaminobenzene sulfonic acid sodium salt(Cl 10385; Acid Orange No. 3), 4-[(2,4-dihydroxyphenyl)azo]-benzene sulfonic acid monosodium salt(Cl 14270; Acid Orange No. 6), 4-[(2-hydroxynaphth-1-yl)azo]-benzene sulfonic acid sodium salt(Cl 15510; Acid Orange No. 7), 4-[(2,4-dihydroxy-3-[(2,4-dimethylphenyl)azo]phenyl)azo-benzene sulfonic acid sodium salt(Cl 20170; Acid Orange No. 24), 4-hydroxy-3-[(4-sulfonaphthalen-1-yl)azo]-1-napthalene sulfonic acid disodium salt (Cl 14720; Acid Red No. 14), 6-hydroxy-5-[(4-sulfonaphth-1-yl)azo]-2,4-napthalene-disulfonic acid trisodium salt(Cl 16255; Ponceau 4R; Acid Red No. 18), 3-hydroxy-4-[(4-sulfonaphth-1-yl)azo]-2,7-napthalene-disulfonic acid trisodium salt (Cl 16185; Acid Red No. 27), 8-amino-1-hydroxy-2-(phenylazo)-3,6-napthalene disulfonic acid disodium salt(Cl 17200; Acid Red No. 33), 5-(acetyl-amino)-4-hydroxy-3-[(2-methyl-phenyl) -azo]-2,7-napthalene disulfonic acid disodium salt (Cl 18065; Acid Red No. 35), 2-(3-hydroxy-2,4,5,7-tetraiodo-dibenzopyran-6-on-9-yl)-benzoic acid -disodium salt (Cl 45430;Acid Red No. 51), N-[6-(diethylamino)-9-(2,4-disulfophenyl) -3H-xanthen-3-yliden]-N-ethyl-ethanaminium hydroxide, inner salt, sodium salt (Cl 45100; Acid Red No. 52), 8-[(4-(phenylazo)-phenyl)azo]-7-naphthol-1,3-disulfonic acid disodium salt (Cl 27290; Acid Red No. 73), 2xe2x80x2,4xe2x80x2,5xe2x80x2,7xe2x80x2-tetrabromo-3xe2x80x2,6xe2x80x2-dihydroxyspiro[isobenzofuran-1(3H),9xe2x80x2[9H]xanthen]-3-one disodium salt (Cl 45380; Acid Red No. 87), 2xe2x80x2,4xe2x80x2,5xe2x80x2,7xe2x80x2-tetrabromo-4,5,6,7-tetrachloro-3xe2x80x2,6xe2x80x2-dihydroxyspiro[isobenzofuran-1(3H), 9xe2x80x2[9H]xanthen]-3-one disodium salt (Cl 45410; Acid Red No. 92), 3xe2x80x2,6xe2x80x2-dihydroxy-4xe2x80x2,5xe2x80x2-diiodospiro-[isobenzofuran-1(3H),9xe2x80x2(9H)-xanthen)-3-one disodium salt (Cl 45425; Acid Red No. 95), (2-sulfo-phenyl)di[4-(ethyl((4-sulfophenyl)-methyl)amino)phenyl]-carbenium disodium salt, betaine (Cl 42090; Acid Blue No. 9; FDandC Blue No. 1), 1,4-bis[(2-sulfo-4-methylphenyl)amino]-9,10-anthraquinone-disodium salt(Cl 61570; Acid Green No. 25), bis[4-(dimethylamino)-phenyl]-(3,7-disulfo-2-hydroxy-naphth-1-yl)-carbenium inner salt, monosodium salt (Cl 44090; Food Green No. 4; Acid Green No. 50), bis[4-(diethylamino)phenyl](2,4-disulfophenyl) -carbenium inner salt, sodium salt(2:1) (Cl 42045; Food Blue No. 3; Acid Blue No. 1), bis[4-(diethyl-amino)phenyl](5-hydroxy-2,4-disulfophenyl)carbenium inner salt, calcium salt (2:1) (Cl 42051; Acid Blue No. 3), 1-amino-4-(cyclohexyl-amino)-9,10-anthraquinone-2-sulfonic acid, sodium salt (Xl 62045; Acid Blue No. 62), 2-(1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-yliden)-2,3-dihydro-3-oxo-1H -indol-5-sulfonic acid disodium salt (Cl 73015; Acid Blue No. 74), 9-(2-carboxyphenyl)-3-[(2-methyl-phenyl)-amino]-6-[(2-methyl-4-sulfophenyl)amino]-xanthylium inner salt, monosodium salt (Cl 45190; Acid Violet No. 9), 1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone sodium salt (Cl 60730; DandC Violet t No. 2; Acid Violet No. 43), bis[3-nitro-4-[(4-phenylamino)-3-sulfophenylamino]-phenyl]-sulfone (Cl 10410; Acid Brown No. 13), 5-amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)-2,7-napthalene disulfonic acid disodium salt (Cl 20470; Acid Black No. 1), 3-hydroxy-4-[(2-hydroxynaphth-1-yl)azo]-7-nitro-1-napthalene sulfonic acid chromium complex (3:2) (Cl 15711; Acid Black No. 52), 3-[(2,4-dimethyl-5-sulfophenyl)azo]-4-hydroxy-1-napthalene sulfonic acid disodium salt (Cl 14700; Food Red No. 1; Ponceau SX; FDandC Red No. 4), 4-(acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-sulfophenyl)azo]naphth-1-yl)azo]-1,7-napthalene disulfonic acid tetrasodium salt (Cl 128440; Food Black No. 1) and 3-hydroxy-4-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazole-4-yl -azo)napthalene-1-sulfonic acid sodium salt chromium complex (Acid Red No. 195).
Suitable cationic dyestuffs include, for example, the following:
9-(dimethylamino)-benzo[a]phenoxazin-7-ium-chloride (Cl 51175; Basic Blue No. 6), di[4-(diethylamino)phenyl][4-(ethylamino)naphthyl]carbenium chloride (Cl 42595; Basic Blue No. 7), 3,7-di(dimethylamino)phenothiazin-5-ium chloride (Cl 52015; Basic Blue No. 9), di[4-(dimethylamino)phenyl][4-(phenylamino) -naphthyl]- carbenium chloride (Cl 44045; Basic Blue No. 26), 2-[(4-(ethyl(2-hydroxyethyl)-amino)phenyl)azo]-6-methoxy-3-methyl-benzothiazolium methyl sulfate (Cl 11154; Basic Blue No. 41), 8-amino-2-bromo-5-hydroxy-4-imino-6-[(3-(trimethyl-ammonio)phenyl)amino]-1(4H)-napthalenone chloride (Cl 56059; Basic Blue No. 99), bis[4-(dimethylamino)-phenyl] [4-(methylamino)phenyl]-carbenium chloride (Cl 42535; Basic Violet No. 1), tris(4-amino-3-methylphenyl)carbenium chloride (Cl 42520; Basic Violet No. 2), tris[4-(dimethylamino) phenyl]carbenium chloride (Cl 42555; Basic Violet No. 3), 2-[3,6-(diethylamino)dibenzopyranium-9-yl]-benzoic acid chloride (Cl 45170; Basic Violet No. 10), di(4-aminophenyl)-(4-amino-3-methylphenyl)carbenium chloride (Cl 42510; Basic Violet No. 14), 1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene (Cl 21010; Basic Brown No. 4), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Cl 12250; Basic Brown No. 16), 1-[(4-amino-2-nitrophenyl)azo]-7-(trimethyl-ammonio)-2-naphthol chloride (Cl 12251; Basic Brown No. 17), 1-[(4-amino-3-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Cl 12251; Basic Brown No. 17), 3,7-diamino-2,8-dimethyl-5-phenyl-phenazinium chloride (Cl 50240; Basic Red No. 2), 1,4-dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1,2,4-triazolium chloride (Cl 11055; Basic Red No. 22), 2-hydroxy-1-[(2-methoxy-phenyl)azo]-7-(trimethylammonio)-napthalene chloride (Cl 12245; Basic Red No. 76), 2-[2-((2,4-dimethoxyphenyl) -amino)ethenyl]-1,3,3-trimethyl-3H-indole-1-ium chloride (Cl 48055; Basic Yellow No. 11), 3-methyl-1-phenyl-4-[(3-(trimethyl-ammonio)phenyl)-azo]pyrazole-5-one chloride (Cl 12719; Basic Yellow No. 57) and bis[4-(diethylamino)phenyl]phenyl carbenium hydrogen sulfate (1:1) (Cl 42040; Basic Green No. 1).
Suitable nonionic dyestuffs (especially for producing an improved color balance and for production of special nuances) include the following:
1-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5), 1-(2-hydroxyethoxy)-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 4), 1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Yellow No. 2), 2-[(2-hydroxyethyl)-amino]-1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 1-(2-hydroxy-ethoxy)-3-methylamino-4-nitrobenzene, 2,3-(dihydroxypropoxy)-3-methylamino-4-nitro-benzene, 2-[(2-hydroxyethyl)amino]-5-nitrophenol (HC Yellow No. 11), 3-[(2-aminoethyl)amino]-1-methoxy-4-nitrobenzene-hydrochloride (HC Yellow no.9), 1-[(2-ureidoethyl)amino]-4-nitrobenzene, 4-[(2,3-dihydroxypropyl)amino]-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 6), 1-chloro-2,4-bis-[(2-hydroxyethyl)-amino]-5-nitrobenzene (HC Yellow No. 10), 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-chloro-4-[(2-hydroxyethyl)amino]-3-nitrobenzene (HC Yellow No. 12), 4-[(2-hydroxyethyl)amino-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 13), 4-[(2-hydroxyethyl)amino]-3-nitrobenzonitrile (HC Yellow No. 14), 4-[(2-hydroxyethyl)amino]-3-nitro-benzamide (HC Yellow No. 15), 1-amino-4-[(2-hydroxyethyl)amino-2-nitrobenzene (HC Red No. 7), 2-amino-4,6-dinitrophenol, 2-ethylamino-4,6-dinitrophenol, 4-amino-2-nitrodiphenylamine (HC Red No. 1), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red No. 13), 1-amino-5-chloro-4-[(2-hydroxyethyl)amino]-2-nitrobenzene, 4-amino-1-[(2-hydroxyethyl)-amino]-2-nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)-amino]-3-nitrophenol, 1-[(2-aminoethyl)amino]-4-(2-hydroxy-ethoxy)-2-nitro-benzene (HC Orange No. 2), 4-(2,3-dihydroxy-propoxy)-1-[(2-hydroxyethyl)-amino]-2-nitrobenzene (HC Orange No. 3), 1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 10), 5-chloro-1,4-[di(2,3-dihydroxypropyl)amino-2-nitrobenzene (HC Red No. 11), 2-[(2-hydroxy-ethyl)amino]-4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 2-chloro-6-methylamino-4-nitrophenol, 2-chloro-6-[(2-hydroxyethyl)amino]-4-nitrophenol, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4-[(3-hydroxypropyl)amino]-3-nitrophenol, 2,5-diamino-6-nitropyridine, 1,2,3,4-tetrahydro-6-nitroquinoline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No. 14), 1,4-bis[(2-hydroxyethyl)amino]-2-nitrobenzene, 1-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)-amino]-benzene (HC Blue No. 2), 1-amino-3-methyl-4-[(2-hydroxy-ethyl)amino]-6-nitrobenzene (HC Violet No. 1), 4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 12), 4-[di(2-hydroxyethyl)amino]-1-[(2-methoxyethyl)amino]-2-nitrobenzene (HC Blue No. 11), 1-[(2,3-dihydroxypropyl)amino]-4-[methyl-(2-hydroxyethyl)-amino]-2-nitrobenzene (HC Blue No. 10), 1-[(2,3-dihydroxypropyl)amino]-4-[ethyl-(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 9), 1-(3-hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene (HC Violet No. 2), 1-methylamino-4-[methyl-(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Blue No. 6), 2-((4-amino-2-nitrophenyl)amino)-5-dimethyl-amino-benzoic acid (HC Blue No. 13), 1,4-di[(2,3-dihydroxypropyl)amino]-9,10-anthraquinone, 1-[(2-hydroxyethyl)amino]-4-methylamino-9,10-anthraquinone (Cl 61505, disperse Blue No. 3), 2-[(2-aminoethyl)amino]-9,10-anthraquinone (HC Orange No. 5), 1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone, 1-[(3-aminopropyl)amino]-4-methylamino-9,10-anthraquinone (HC Blue No. 8), 1-[(3-aminopropyl)amino]-9,10-anthraquinone (HC Red No. 8), 1,4-diamino-2-methoxy-9,10-anthraquinone (Cl 62015, disperse Red No. 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis[(2-hydroxyethyl)amino]-9,10-anthraquinone (Cl 62500, Disperse Blue No. 7, Solvent Blue No. 69), 1-[di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]-benzene (Cl 11210, disperse Red No. 17), 4-[(4-aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzene (HC Yellow No. 7), 2,6-diamino-3-[(pyridine-3-yl)azo]pyridine, 2-((4-(acetylamino)phenyl)-azo)-4-methylphenol (Cl 11855; Disperse Yellow No. 3).
From the group of direct-dyeing dyestuffs 2-amino-4,6-dinitrophenol, 2-ethylamino-4,6-dinitrophenol, 2-[(2-hydroxyethyl)amino]-4,6-dinitrophenol and dyestuffs of the general formula (II): 
wherein R is hydrogen, methyl, ethyl or hydroxyethyl, are especially preferred.
The total concentration of direct-dyeing dyestuffs in the composition according to the invention amounts to about 0.1 to 10 percent by weight, preferably about 0.1 to 5 percent by weight.
Understandably the dyestuffs, in so far as they are bases, can also be used in the form of their physiologically compatible salts with organic or inorganic acids, for example hydrochloric acid or sulfuric acid, and/or, in so far as they have an aromatic OH group, in the form of their salts with bases, for example as alkali phenolates.
The above-described combinations of the compounds of formula (I) with oxidative hair dye pre-cursor compounds and/or direct dyeing dye compounds are applied for dyeing in a suitable dye carrier.
Furthermore additional conventional additive ingredients can be included in the compositions according to the invention. These additive ingredients can, for example, include antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, as well as perfume oils, penetration agents, buffer systems, complex formers, preservatives, wetting agents, emulsifiers, thickeners and care materials.
The form of the dye composition according to the invention can be a solution, especially an aqueous or aqueous/alcoholic solution. However compositions according to the invention in the form of a creams, a gel or an emulsion are especially preferred. Their composition includes a mixture of dyestuff components with conventional cosmetic additive ingredients suitable for this sort of preparation.
Conventional additives for solutions, creams, emulsion or gels include, for example, solvents, such as water, lower aliphatic alcohols, for example, ethanol, propanol or isopropanol, glycerol or glycols, such as 1,2-propylene glycols; wetting agents or emulsifiers from the classes of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants, such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzene sulfonates, ethoxylated nonylphenols, fatty acid alkanolamides and ethoxylated fatty acid esters; thickeners, such as higher fatty alcohols, starches, cellulose derivative compounds, petrolatum, paraffin oils and fatty acids, as well as care materials, such as cationic resins, lanolin derivative compounds, cholesterol, pantothenic acid and betaines. The above-mentioned ingredients are used in a common amount suitable for their purposes, for example the wetting agents and emulsifiers are used in a concentration of about 0.1 to 30 percent by weight, the thickeners in an amount of about 0.1 to 30 percent by weight the care materials in a concentration of about 0.1 to 5.0 percent by weight.
The ready-to-apply or ready-to-use hair dye mixture according to the invention is prepared by mixing the dye composition containing at least one compound of formula (I) together with an oxidizing agent just prior to use.
The oxidizing agent used for this type of dye composition is mainly hydrogen peroxide or its addition compounds with urea, melamine, sodium borate or sodium carbonate. Primarily an oxidizing composition is mixed with the dye composition, which is a 3 to 6 percent aqueous solution of hydrogen peroxide or its addition compounds. The weight ratio of the dye composition to the oxidizing composition in the mixture is preferably about 5:1 to 1:3, especially preferably from 1:1 to 1:2. Larger amounts of oxidizing agent, above all, are used when the dyestuff concentration in the hair dye composition is higher, or when a stronger bleaching of the hair is intended. It is also possible to use air oxygen for oxidation of the dyestuff instead of the above-described oxidizing composition.
The pH value of the ready-to-apply or ready-to-use hair dye mixture according to the invention is determined by the alkali content in the dye composition and the acid concentration in the oxidizing composition. The pH of the dye composition is from about 6 to about 11.5 and the pH of the oxidizing composition from about 2 to about 6.5. According to its composition the dye composition according to the invention can react like a weak acid, neutral composition or like an alkaline composition. The pH of the ready-to-apply or ready-to-use hair dye mixture is then from about 3 to 11, preferably from 5 to 10. The basic pH adjustment occurs preferably with ammonia, however also with organic amines, for example 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, monoethanolamie and triethanolamine or also inorganic bases, such as sodium hydroxide and potassium hydroxide. Inorganic or organic acids, such as phosphoric acid, acetic acid, lactic acid, ascorbic acid, citric acid or tartaric acid, can be used to adjust the pH in the acid range.
Subsequently when dyeing hair with the ready-to-apply or ready-to-use hair dye mixture according to the invention it is applied to the hair in an amount sufficient for the dyeing of the hair, according to the abundance of the hair, usually about 60 to 200 grams. Then the mixture is allowed to act on the hair for a sufficient time interval at about 15xc2x0 C. to 50xc2x0 C., preferably at about 30xc2x0 C. to 40xc2x0 C., for about 10 to 45 minutes, preferably about 30 minutes. Subsequently the mixture is rinsed from the hair and dried. The hair is optionally washed with a shampoo, if necessary, and optionally after-rinsed with a weak organic acid, for example citric or tartaric acid. Then the hair is dried.
The dye compositions according to the invention containing the 4,5-diaminopyrazoles of formula (I) provide hair dyeing with outstanding color fastness, especially light fastness, wash fastness and rubbing fastness. In regard to their color-imparting properties the hair dye compositions according to the invention provide a broad palette of different color shades, especially in the fashionable red range, according to the type and amounts of the various dye compound ingredients. A special color intensity and brightness characterize the color shades produced according to the invention. Very good color properties are provided by the dye composition according to the present invention. Particularly the hair dye composition also provides uniform and maintainable good dyeing on pre-damaged hair, which has been damaged to various different extents.
The following examples illustrate the above-described invention in more detail, but the details in these examples should not be considered as limiting the claims appended hereinbelow.